U.S. patent number 3,725,351 [Application Number 05/064,052] was granted by the patent office on 1973-04-03 for fibers of polyesters prepared from ethylene glycol, dimethyl terephthalate, sodium dimethyl-5-sulphoisophthalate and poly(ethylene oxide).
This patent grant is currently assigned to Imperial Chemical Industries Limited. Invention is credited to Albert Keith Harrison, John Mather.
United States Patent |
3,725,351 |
Harrison , et al. |
April 3, 1973 |
FIBERS OF POLYESTERS PREPARED FROM ETHYLENE GLYCOL, DIMETHYL
TEREPHTHALATE, SODIUM DIMETHYL-5-SULPHOISOPHTHALATE AND
POLY(ETHYLENE OXIDE)
Abstract
Fibers of copolyester of improved affinity for dyestuffs are
derived from at least one dicarboxylic acid and at least 2 glycols,
one of the glycols being a poly (alkylene oxide) and a proportion
of the structural units of the copolyesters consists of organic
radicals containing at least one sulphonate group as the metal
salt.
Inventors: |
Harrison; Albert Keith
(Harrogate, EN), Mather; John (Harrogate,
EN) |
Assignee: |
Imperial Chemical Industries
Limited (London, EN)
|
Family
ID: |
26267538 |
Appl.
No.: |
05/064,052 |
Filed: |
July 23, 1970 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
783423 |
Dec 12, 1968 |
|
|
|
|
Current U.S.
Class: |
528/295; 8/922;
525/437; 8/539; 524/341 |
Current CPC
Class: |
C08G
63/6886 (20130101); C08G 63/6884 (20130101); C08G
63/672 (20130101); C08G 63/668 (20130101); Y10S
8/922 (20130101) |
Current International
Class: |
C08G
63/672 (20060101); C08G 63/668 (20060101); C08G
63/00 (20060101); C08G 63/688 (20060101); C08g
017/14 () |
Field of
Search: |
;260/49,75S |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Short; William H.
Assistant Examiner: Lee; L. L.
Parent Case Text
This application is a continuation of Ser. No. 783,423, filed Dec.
12,1968, and now abandoned.
Claims
We claim:
1. A fiber whose fiber-forming material consists of the product of
the process of reacting ethylene glycol and dimethyl terephthalate
under ester-interchange conditions to form poly(ethylene
terephthalate) prepolymer, thereafter adding to this prepolymer
poly(ethylene oxide) with a molecular weight of from about 500 to
about 6000 and sodium dimethyl-5-sulphoisophthalate, and thereafter
polycondensing said reaction mixture, whereby a copolyester is
formed wherein at least 75 percent of the recurring structural
units are ethylene terephthalate units, from 0.5 to 10 structural
units per 100 total structural units are organic radicals derived
from said sulphoisophthalate, and from 1 to 15 structural units per
100 total structural units are organic radicals derived from said
poly (ethylene oxide).
2. The fiber of claim 1, wherein said poly(ethylene oxide) has a
molecular weight of about 1540.
Description
This invention relates to copolyesters of improved affinity towards
basic dyestuffs.
According to the present invention we provide an improved, film or
fiber-forming copolyester derived from at least one dicarboxylic
acid and at least two glycols wherein one of the glycols is a
poly(alkylene oxide) and of which a minor proportion of the
structural units consists of organic radicals containing at least
one sulphonate group in the form of the metal salt.
Suitable glycols other than poly(alkylene oxide) from which the
copolyesters of our invention may be derived are, for example,
HO(CH.sub.2).sub.n OH where n is not less than 2 and not greater
than 10 and 1:4-bis(hydroxymethyl) cyclohexane.
Preferably the copolyesters of our invention should contain in
their molecule from one to 15 units derived from poly(alkylene
oxide) per 100 total units.
By "minor proportion" we mean from one to 20 per 200.
The poly(alkylene oxide) from which the units are derived may have
molecular weight from 500-20,000 but is preferably of molecular
weight 500-6,000. Below a molecular weight of 500, the
poly(alkylene oxide) is sufficiently volatile that it tends not to
remain in the copolyester reaction mixture during reaction.
The copolyesters of our invention may be prepared by a variety of
methods of which the following may be taken as examples:
A. The reaction of a dicarboxylic acid with a diol in the presence
of a minor proportion of a sulphonated dicarboxylic acid or a
sulphonated diol and a minor proportion of a poly(alkylene
oxide).
B. The reaction of a copolyester containing sulphonated units with
a poly(alkylene oxide).
C. The reaction of a copolyester containing poly(alkylene oxide)
units with a sulphonated dicarboxylic acid or a sulphonated
diol.
D. The melt-blending of a copolyester containing sulphonated units
with a copolyester containing poly(alkylene oxide) units.
In general the metal salt of the sulphonate group should be that of
an alkali metal or an alkaline earth metal, although other metals
may be used. Preferably the sulphonate groups should be in the form
of the metal salt during the polycondensation stage.
Particularly useful are copolyesters of which no less than 75
percent of the units are ethylene terephthalate units or are
ethylene bis-1:2-(paracarboxyphenoxy)ethane units.
The copolyesters of our invention may additionally contain other
additives commonly added to polyesters and in the amounts commonly
used. In particular we have found the presence of an antioxidant
and a stabilizer against adverse effects of irradiation to be
beneficial.
The copolyesters of our invention may be processed to fibers by any
known process. The fibers so formed have affinity towards basic
dyestuffs superior to that of a copolyester containing sulphonated
units but no poly(alkylene oxide) units and also superior to that
of a copolyester containing poly(alkylene oxide) units but no
sulphonated units, and that the extent of this superiority is
greater than the additive effect expected for the individual
factors, that is poly(alkylene oxide) and sulphonated units.
In order that the process of our invention should be the more fully
understood, we give hereinafter examples of methods in which it may
be put into practice. In these examples, all parts are by weight.
By Viscosity Ratio we mean the ratio .eta./.eta.o where .eta. is
the viscosity of the solution of polymer and .eta.o is the
viscosity of the pure solvent. Determinations of Viscosity Ratio
were carried out at 25.degree. C in orthochlorophenol at a
concentration of 1 g. of polymer to 100 ml. of solvent.
EXAMPLE 1
A mixture of dimethyl terephthalate (194 parts), ethylene glycol
(155 parts) and manganese acetate (0.0486 parts) was heated at a
temperature of 220.degree. C for 11/2 hours, after which time the
theoretically obtainable quantity of methanol for full reaction had
distilled off from the mixture. To the resultant reaction mixture
there were added antimony trioxide (0.078 parts) and triphenyl
phosphite (0.26 parts) and the resultant mixture heated for 3 hours
at 284.degree. C under an atmosphere of nitrogen at a pressure of
0.2 mm of mercury, under normal poly-condensation conditions. The
resultant polyester had Viscosity Ratio 1.6, as determined as
described hereinbefore.
A portion of the polyester so obtained was dried at 135.degree. C
for 3 hours, formed into a candle at 220.degree. C and melt-spun
into fibers. The resultant fibers were drawn over a pin at
85.degree. C and a plate at 165.degree. C, using a draw ratio of
4.0 to 1.
The drawn fiber (100 parts) was subjected to dyeing at 100.degree.
C for 1 hour in a dyebath of the composition:
Dyestuff of Color Index Red 14 12.5 parts Sodium sulphate 600 parts
Water 7,500 parts
and containing diphenyl (0.5 parts per 100 ml. of dye liquor) as
carrier. Only a very weak shade of dyeing was obtained.
EXAMPLE 2
A copolyester was prepared by following the procedure of Example 1
exactly, with the distinction that immediately prior to the
polycondensation stage there were added to the reaction mixture
sodium dimethyl-5-sulphoisophthalate (5.92 parts) and poly(ethylene
oxide) of molecular weight 1540 (9.7 parts). The resultant
copolyester therefore contained sulphonate-bearing structural units
and poly(ethylene oxide) units. The resultant copolyester was spun
and drawn as described in Example 1 and subjected to the same
dyeing conditions with the same dyestuff. A deep shade of dyeing
was obtained.
EXAMPLE 3
Comparative experiments were carried out adding on the one hand
dimethyl-5-sulphoisophthalate (5.92 parts) only and adding
poly(ethylene oxide) of molecular weight 1540 (9.7 parts) only.
These experiments showed that the fibers of Example 2 had greater
affinity towards the basic dyestuff than would be expected from the
additive effect of linkages derived from
dimethyl-5-sulphoisophthalate and those derived from poly(alkylene
oxide), showing a synergistic effect of the two factors.
* * * * *